Process for resolving petroleum emulsions



35 I H represents the oxy acyl radical derived'from such (ornncoonmimi acid, i. e., the ordinary acid radical. Blown oils m represents the numeral 0, 1, or 2, and m" copending applicationfor patent, Ser. No. 206,904,

Patented July 18, 1$3 I I pastas erases rarestseries Melvin De Groote, University City, M0,, aseianor,

by mesne assignments, to Petrolite Comratlon, Ltd, a corporation oi Delaware y No Drawing. Application May 31,1938,

Serial No. mass 6 Claims. (01. lac-s) This invention relates to the treatment of emulrepresents the numeral 0, 1, or 2, with the proviso sions of mineral oil and water, such as petroleum that m+m'+m"=3. emulsions, and has for its object to provide a However, the radical 03H; which appears in novel process for resolving or breaking petroleum the above formula. may represent any similar 5 emulsions of the .water-in-oil type into their radical, such as a CsH radical, CiHa radical, etc. 5

.component parts of oil and water or brine. and therefore the above formula may be vre- The treating agent or demulsifying agent em- 'wrltten: ployed in the present process is a new composition of matter consisting of a certain kind of Mood u complex amine derived by reaction between (a) 1 v acid esters obtained by reaction between phthals ated triricinolein, phthalated ricinoleic acid, or where n represents a. small whole number prefsimilar materials; and (b) simpler amines of erably not over 10. the kind hereinafter described, and the process In the above formulas, T represents a nonl5 involves subjecting a petroleum emulsion of the hydroxy aliphatic hydrocarbon radical, such as a water-in-oil type to the action of said demulsifymethyl, ethyl, propyl, amyl, or similar radical; or ing agent, so as to cause the emulsion to break T may represent a non-hydroxy alicyclic radical, down and separate into its component parts of such as a cyclohewl radical, or a non-hydroxy' oil and water or brine when the emulsion is peraralkylradical, such as .a benzyl radical; or the m mitted to remain in a quiescent state after .acylated radical obtained by replacing ahydro n treatment or is subjected to other equivalent atom of the hydroxyl grounof an alkylol radical separatory procedures. by the'acyl radical of a monobasic carboxy acid,

Inasmuch as the demulsifying agent employed such as acetic acid, butyric acid, oleic acid, stearic. in my process constitutes a new chemical comacid, naphthenic acid, abietic acid, or the like, pound or. new composition of matter, I deem it all of which are characterizedby having less advisable to describe the raw materials entering than 32 carbon atoms. The alkylol radical prior into the manufacture of the same, as well as the to acylation may be a hydroxy alicyclic or a method of manufacture. hydroxy aralkyl radical, provided that the hy- One can obtain or manulacturechemical comdroxy radical is attached to the aliphatic residue pounds whose composition is indicated by the of the aralkyl radical. In the aboveiormulas, 30 following formulas: v OHRCQOH represents a hydroxylated fatty acid, 1

n such as ricinoleic acid, hydroxystearic acid, diommoonmm/ hydrowstearic acid, diricinoleic acid, tririclnoleic acid, polyricinoleic acid, etc.; and OHRCOO .(omncoogmom (oxidized oils) are not included. As to the amines above described which happen to be tertiary amines, it may be well to point out 40 033000-0534 i that these maybe formed readily by a reaction in ,0 volving an ester of the hydroxylated' fatty acid T and a corresponding amine. This may beillus- N/ trated in the following manner: 0H.B000.C:Hi

onncoonc=nt+ oac=m m+ r (OH.R.COO.C2H4)3N Q Reference is made to copendingapplication The compo ds a o e de c e y e 511111- for patent, Ser. No. 180,993, filed December 21, marized by the fo owing formula: 1937, by Melvin De Groote, Bernhard Keiser, and

5 3 Charles M. Blair, Jr. If triethanolamine as em- (033000 CBHOnN/ ployed in the above formulas is replacedby ethyl a diethanolamine or .by diethyl ethanolamine then one would readily obtain the other two types of in which on represents the numeral 1, 2, or 8, tertiary amines illustrated. Reierenceis made to decyl ethanolamine,

filed May 9, 1938, by Melvin De Groote, Bernhard Keiser and Charles M. Blair, Jr.

In the remaining three types of materials there is at least one amino. hydrogen atom present. The manufacture of such type material may be illustrated by the following reactions:

Similar reactions to the one immediately preceding result in compounds, such as:

OH.R.CO OLCQHA However, if maximum yields are not necessary, one need not resort to reactions of the kind previously described to produce amines having at least one amino hydrogen, but one may employ the following reactions:

OH-CiEl NH 0H.R.G00\ OH' 03H OH.R.COOCa I 011.0234 03.3.000

NH- 3(gg.R.( J 0 0.O,Hi):N on.n.coo +on.o,m h

oER.Co0-Cl l 0110,11; onao'oo /NH Naturally if ethyl ethanolamine or a similar amine were to 'replace ethanolamine (mono-- ethanolamine), one would obtain the remaining type of amine above illustrated.

Suitable hydroxy primary and secondary amines which may be employed to produce materials of the kind above described include the following: diethanolamine, monoethanolamine, ethyl ethanolamine, methyl ethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc. Other examples include cyclohexanolamine, dicyclohexanolamine, cyclohexyl ethanolamine, cyclohexyl propanolamine, benzyl ethanolamine, benzyl propanolamine, pentanolamine, hexanolamine, octyl ethanolamine, octacyclohexanolethanolamine,

etc.

Similarly, suitable hydroxy tertiary amines which may be employed include the following: triethanolamine, diethanolalkylamines, such as diethanol ethylamine, diethanol propylamine, etc. Other examples include diethanol methylamine, tripropanolamine, dipropanol methyl- H OH. RCOO.O.H1-)-N (T)-II in which n represents a small whole number, preferably less than 10, and m represents the nu- I meral 1, 2, or 3, 1n represents the numeral 0, 1, or 2, and m represents the numeral 0, 1 or 2,

with the proviso that m+m'+m"=3, have four common characteristics. In the first place, these amines are not quaternary ammonium bases or salts thereof. The expression quaternary ammonium is properly and conventionally applied to compounds in which all four hydrogen atoms of the ammonium radical NH; have been replaced by a hydrocarbon radical or oxy-hydrocarbon radical, as, for example, in trimethyl phenyl ammonium hydroxide.

Secondly,- an important characteristic which must be recognized is that these amine compounds are not amides. It is to be noted that an amide formation involves a product in which there is a direct linkage between the carboxylic carbon atom and the nitrogen atomin the amine. This is not the case in the compounds employed as intermediate raw materials for production of the compounds used as demulsifying agents in the present process.

In the third place, it must be recognized that these compounds are derived only from basic amines. The word basic is employed to exclude amines having little or no basicity such as the ordinary aromatic amines or any amine having at least one aryl radical directly joined to the amino nitrogen atom. For this reason, these amine products which are herein contemplated as demulsifying agents in the resolution of petroleum emulsions and which necessarily are characterized by freedom from any aryl groups as such, cannot be derived from aryl amines. They are derived solely from alkyl, alicyclic, or aralkyl amines having at least one hydroxyl group present. It is true that in the aralkyl amines there is an aryl group present, but it is not directly attached to the nitrogen atom as in the case of aryl amines but in fact represents nothing more or less. than a substituted alkylamine. For instance, I consider benzylamine as being the primary amine, phenmethyl amine.

Finally, it must be recognized that these materials have not lost any basicity in the forms of the esterified amine and that they exhibit all the properties of a basic amine, that is, they combine with water to form a base presumably a substituted ammonium compound, but not quaternary ammonium compounds insofar that there are always one, two or three unsubstituted hydrogen atoms of the ammonium radical present. They combine with various acids to form salts. For example, they may be combined with acetic acid, hydrochloric acid, lactic acid, chloracetic acid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or any suitable organic or inorganic acid, to form salts. It is understood thatthe reference in the specification and appended claims to the amines includes the basic form and the acid salts as well as the amines themselves. The characteristic demulsifying properties of the new compositions of matter herein describedare contributed in part by the amine, and it is immaterial whether the amine maybe considered as being in any one of the following forms:

in which T represents the substituents for theamino hydrogen atoms of the parent ammonia from which all amines are hypothetically derived and X simply represents theacid radical of any acid employed. This statement applies with equal force and effect to the final product, or composition of matter, which is also a basic amine of a more complex type.

Reference is again made to the formula which summarizes the various amines used as intermediate raw materials, viz.:

(QH.Ro0o .o,.Hz.)..N

- I in which the characters have their previous significance.

Attention is directed to the fact that where the substituted alkyl radical -OH.R.CO0.C2H4* appears, a suitable non-aryl radical other than an aliphatic residuemay serve as the functional equivalent; for instance, an alicyclic radical derived-from a cyclohexyl radical or an aralkyl radical derived from. a benzyl radical. In other words, in the hereto appended claims reference to the CnHinradical as such or as an alkyl radical or residue is intended in the broad sense to include the alicyclic radicals or residues or the aralkyl radicals or residues which are the equiva-- lent thereof. There is no intention to include an aromatic radical where there is a directlinkage between the aromatic nucleus and the amino hydrogen atom for the reason that such products have little or no basicity and do not have the characteristic properties of the amines previously described.

In indicating the various. hydroxylated tertiary amines of the non-aryl type which may be -employed to produce the amine contemplated as the demulsifying agent of thepresent process, it is desirable to indicate that amines of the type where a hydroxy acyl radical replaces a hydrogen atom of a hydroxyl radical of the hydroxy tertiary amine, are not included within the broad alkyl radical.

class of hydroxy tertiary amines unless there is another hydroxyl radical "attached to the usual For instance, if diethyl amino ethanol is treated with lactic acid so as to form laziiyl ethanol diethylamine of the following form a:

then it is understood that such materials would not represent a hydroxy tertiary amine within the meaning or scope as herein employed. If, on the other hand, triethanolamine were treated with lactic acid so as to give monolactyl triethanolamine of the following composition:

then such compound would be included due to the presence of one or more hydroxyl radicals attached to the alkyl radicals.

Similarly, in indicating the various hydroxylated primary or secondary amines of the non-' aryl type which may be employedto produce the amine contemplated as the'demulsifying agent of the 'presentprocess, it is desirable to indicate that amines of the type where a hydroxy acyl radical replaces the hydrogen atom of the hydroxyl radical of a hydroxy primary or secondary amine, are not included within the broad class of hydroxy tertiary amines unless there is another hydroxyl radical attached to the usual lactic acid. If on the other hand, diethanolamine were treated with lactic acid so as to give monolactyldiethanolamine of the following composition:

onions-04:111.

. HO.C:H4 then such compound would be included due to the presence of the hydroxyl radicals attached to the allwl radicals.

The manufacture of compounds from tertiary amines is relatively simple because no precautions are necessary to prevent amidification. The selected fatty oil and the selected hydroxy tertiary amine are mixed insuitable proportions and heated at some point above the boiling point of water, for instance'C., and .at a point below the decomposition point of the amine or the fatty oil, for instance; C., for asuitable period of time, such as two to eight hours. Mild agitation is employed. A catalyst such as. sodium oleate, sodium carbonate, caustic-soda, etcr, may-be present in amounts of about one-half of 1% or less. It is noted that the fatty acids are were derived from diethanolamine, provided that both hydroxy radicals had been esterified with employed in this instance in the form of an ester, to-wit, the glyceride, although as previousy pointed out, other functional equivalents can is readily employed with equal facility. It is to )e noted that the reactions above described do iot take place to any appreciable extent if the 'atty acid has been converted into the soap or :alt. Such salts are not functional equivalents.

When, however, one is employing a hydroxy irimary or a hydroxy secondary amine, precauions must be taken so that one gets a substan- ;ial percentage of products derived by esterificaion rather than amidification. Any suitable es- ;er may be employed, but it is often most convenient to use the glyceride, for instance, triricinolein.

The selected glyceride and the selected hylroxy primary or secondary amine are mixed in iuitable proportions and heated at some point ibove the boiling point of water, for instance, L10 C., and below the decomposition point of he amine or fatty material, for instance, 180 C., or a suitable period of time, such as four to lwenty-four hours. Mild agitation is employed. catalyst such as sodium oleate, sodium car- )onate, caustic soda, etc., may be present in amounts of about or less. It is to be noted ;hat the fatty acids are present in ester form and not in the form of the free acid, and thus ,here is no tendency to form the salt to any narked extent, and if conducted at the lower 'ange of reaction temperatures, there is a de- :ided tendency to form the esterification prodicts rather than the amidification products.

In order to illustrate suitable examples of. the nnines which may be used as intermediate raw naterials the following examples are given:

Intermediate amine-Example 1 Castor oil is employed. For sake of conveniance, its molecular weight is considered as being )25. Commerical triethanolamine and castor oil n the proportion of one mole of castor oil to one nole of triethanolamine are heated at a tempera- ;ure between 150 and 180 C. for about 2 hours. .l/Iild agitation is employed. The reaction prodict so produced may be used as such or may be :onverted into the acetate or other suitable form. The product is characterized by freedom from ."ion-esterified alkylol radicals;

Intermediate amine---E:rample- 2 Polyethanolamine: Y

C2H4O 1140 E N-C$H4O CzH4OH 01H) CgHqDH is substituted for triethanolamine in Example 1.

Intermediate amine-Ea:ample 3 Ethyl dihydroxy stearate is reacted in the previous manner with the various amines above enumerated in Examples 1 and 2. In this case three moles of ethyl dihydroxy stearate is reacted with one mole of the tertiary hydroxyamine.

Intermediate amine-Example 4 Methyl hydroxy stearate is employed to replace ethyl dihydroxy stearate in the examples indicated under Example 3 above.

Intermediate amine-E xample 5 Castor oil (trn'icinolein) is employed. For convenience its molecularweight is considered as being 925. Commercial diethanolamine and castor oil in the proportion of two moles of castor oil to three moles of diethanolamine are heated at a temperature of 120-140 C..f0r about 12 hours. Mild agitation is employed. Loss of basicity is an indication of amldification. Time of reaction may be extended or temperature lowered or raised so as to insure maximum esterification. The reaction product so produced may be used as such or may be converted into the acetate or other suitable form. The product should be free from nonesterified alkylol radicals.

Intermediate amine-Example 6 Ethanolamine is substituted for diethanolamine in Example 1, using three moles of ethanolamine for one mole of castor oil.

Intermediate aniineExample 7 Ethyl ethanolamine is substituted for diethanolamine in Example 1, using three moles of ethyl ethanolamine for one mole of castor oil.

Intermediate amine- -Exampl'e 8 An ether amine of the following composition:

CzHAOCQEHOH is substituted for diethanolamine in Example 5.

Having prepared the relatively simpler intermediate amine of the kind previously described, the second step in the preparation of the new composition of matter is to produce acid mters of the kind obtainable by reaction between polybasic carboxy acids or their functional equivalents, such as the anhydrides, and hydroxylated fatty acids, esters, or the like.

The manufacture of this class of materials is well known because they have been used extensively in the manufacture of demulsiflers, plasticizers, and the like. The most readily available hydroxylated fatty body is castor oil, which consists of about 85% triricinolein. One of the most suitable di'basic acids is phthalic acid because of its low cost, stability towards heat, etc. If triricinolein be indicated by the following formula:

A OH.R.COO.CH1

OH.R.CO0.CH

orracooom then reaction products of phthalic anhydride or phthalic acid 'may be indicated in the following manner, although for purposes of convenience, phthalic acid is notshown in the form of the usual isomer, where, of course, the two carboxyl radicals are attached to adjacent carbon atoms:

B COOH 0H.R.ooo.c11'

OH.R.COO.CH:

COOH

COO.R..COO.CH2

C HO.R.COO.CH

00001! COO.R.COO.CH:

@OOJLCOQCH: COOH 000011 COO.R.COO.(|]H: 600011000 011 A large number of related products immediately v present themselves, for instance, esters derived by to the glycol radical or residue.

reaction with ricinoleic acid, hydroxystearic acid, dihydroxy stearic acid, and the like; or the corresponding esters derived from glycols or glycol ethers such as ethylene glycol or diethylene glycol which contain no free hydroxyl radicals attached Similarly, one

' might have products derived from monohydric alcohols, for instance, ethyl ricinoleate, propyl the acidity of one of the carboxylic hydrogen atoms or two of the. carboxylic hydrogen atoms,

- in anyfeasible manner, that is, by neutralization with an alkali or by conversion into an ester involving reaction with a new kind of an alcohol, i. e., a monohydric, dihydric, trihydric, etc.

In the case of D above, two carboxylic hydrogens may be neutralized. In any event, however, the material derived by reaction between a polybasic acid or its functional equivalent and a hydroxylated fatty material of the kind described, is characterized by the presence of at least one free carboxyl radical.

Where reference is made to ricinoleic acid, hy-

-droxystearic acid, dihydroxystearic acid, a hydroxy fatty acid, and the like, it is evident that certain simple derivatives, such as the halogenated compounds, etc., are the obvious 'func tional equivalents; for instance, chlorinated triricinolein may be employed instead of triricinolein. Brominated ricinoleic acid might be employed instead of ricinoleic acid. In these instances the hydroxylated fattymaterial, notwithstanding modifications of the kind indicated, still has the same functional properties as the-unmodified hydroxylated fatty material and thus acts in the same manner as far as chemical reactions noted are concerned, and also as far as producing an efiective demulsifying agent is concerned. In the hereto appended claims reference to a hydroxylated fatty material includes such obvious functional equivalents The polybasic acids which may be employed, including some having at least three carboxyl 2,1oc,4s1

. radicals, are phthalic, succinic, malic, fumaric,

Example 2 described previously.

citric, maleic, adipic, tartaric, glutaric, diphenic. naphthalic, oxalic, etc. 1 V

As to the manufacture of materials of the kind described by reactions involving the polybasic carboxy acids or their equivalent, reference is made to the following patents, although it is not intended to infer that such patents describe these materials exclusively. However, they make such reference to the type of reaction involved that a skilled chemist would readily note the description which is particularly pertinent to the type of material just referred to: United States PatentNo. 1,976,602 to De Groote, Adams and Keiser, dated October 9, 1984; United .States Patent No. 1,977,146, to Roberts, dated October 16, 1934.

Composition of matter-Example 1 Castor oil is reacted with triethanolamine (see Example 1 in the previous group of examples),

so as to produce .material corresponding to (OH.R..COO.C2H4) 3N, in which OH.R.COO ;ep re sents the ricinoleic acid radical. One molecular weight of this material is reacted with three molecular weights of diphthalated triricinolein,

See Formula C above. 'This is a conventional esterlflcation reaction, and the materials are in timately mixed and heated at approximately 120-160 C. with constant agitation, until samples taken from the batch and analyzed show substantially complete disappearance of the hy-' droxyl value. A suitable solvent may be present, and water. formed may be distilled oif continuously during the esterification process. The solvent may remain behind in the final product or be removed if desired.

Comosition of matter-Example 2 A similar material is prepared employing polyethanolamine in place of triethanolamine. See

Composition of matter-Example 3 The amine obtained in the manner described in Example 3 above is employed in place of the one obtained by reaction involving castor oil and.

a triethanolamine as described in Composition of matterExample 1.

Composition of matter-Example 4 Dimaleated triricinolein is substitutedfor diphthalated triricinolein-in Composition of matterExamples 1, 2 and 3, immediately above.

Composition of matter-Example 5 Dicitrated triricinolein is substituted for diphthalated triricinolein in Composition of matter-Examples 1, 2 and 3 immediately above. v

Compos'ition of matterE.'rample 6 Triphthalated triricinolein (see .Formula D above) is substituted for diphthalated triricinolein in Composition of matterExamples 1, 2 and 3 immediately above.

Composition of matter-Example 7 'Ifhe' amine obtained by a reaction between di-. ethanolamine instead of triethanolamine (see Intermediate amine-Example 5 above) is substituted'for the product obtained by reaction between triethanolamine and castor oil-in previous Compositionof matter-Examples 1 to 6 inclu sive, with suitable change in molecular proportions. i

, It should be noted, however, that this particular product contains only two hydroxyl radicals available for esteriflcation per atom of nitrogen, andthe' proper adjustment in molecular proportions should be made. Insofar that some amidification may take place in following the directions in preparing the amine from diethanolamine in Intermediate amine-Example 5 above, it is probably the safest procedure to determine the acetyl or hydroxyl value before reacting in molecular proportions so as to leave a residual free carboxyl radical rather than base the mixture of reacting compounds on theoretical stoichiometrical proportions.

Composition of matter-Example 8 Monophthalated'hydroxystearic acid is substituted in Example 1 above, employing three moles of monophthalated hydroxystearic acid and one mole of the product derived by complete esterification of triethanolamine by ricinoleic acid radicals.

Composition of matterExample 9 Two moles of dihydroxystearic acid are treated with one mole of phthalic anhydride so as to eliminate completely any free carboxyl radicals attached to the phthalic anhydride or phthalic acid residue. Three moles of this product so obtained are reacted with one mole of the product derived by complete esterification of triethanolamine by ricinoleic acid radicals. (See Example 1 above.)

Composition of Matter-Example 10 Two moles of monophthalated hydroxystearic acid and one mole of the product derived from diethanolamine and castor .oil (see Composition of matter--Example 7) are reacted in the same manner as described previously.

Composition of Matter-Example 11 Two moles of dihydroxystearic acid are treated with one mole of phthalic anhydride so as to eliminate completely any free carboxyl radicals attached to the phthalic anhydride or phthalic acid residue. Two moles of this product so obtained are reacted with one mole of the product derived by esterification of diethanolamine in the manner described in Composition of matter- Examples 7 and 10 preceding.

Attention is directed to the fact that the alkylolamines are obtained in such a manner that they may be looked upon as being derivatives of dihydric alcohols, for instance, the chlorhydrin of the dihydric alcohol, as indicated in the following manner:

mifs' iiiii As previously stated, the C2H4 radical may be any one of a number of hydrocarbon radicals which are aliphatic, alicyclic, or aralkyl in nature.

It is at once manifest that similar derivatives are available from glycerols, polyglycerols, and the like, as indicated by the following reaction:

'It is not necessary to point out that the same types of reactions will produce secondary or tertiary amines and that the reaction is not limited to a combination with ammonia, but may take place with a combination of other primary or secondary amines, such as amylamine, diamylamine, cyclohexylamine, dicyclohexylamine, benzzlamine, dibenzylamine, amyl cyclohexylamine, e c.

This means that in the type of material previously described, there is a wide variety of ma;- terial, such as monoglycerylamine, diglycerylamine, monoglyceryl diethylamine, monoglyceryl dipropylamine, diglyceryl propylamine, triglycerylamine, etc., which are functional equivalents of the various amines previously described for reaction with triricinolein and the like. When such amines are employed instead of the radical CnH2n appearing in a compound, one'would have in place thereof the radical -OH.C3Hs--; or in case the hydroxyl radical of these OH.C3H5- radical had been removed by esterification' with any available carboxyl, then the substituent which replaces the -CnH2n-- radical might be indicated by the formula D.C3H5-. All that has been said here in regard to functional equivalents will be perfectly obvious without further explanation to those skilled in the art. See United; States Patent No. 2,091,704, dated August 31, 1937, to Duncan and McAllister, and also United States Patent No. 2,042,621, dated June 2, 1936, to Olin.

Similarly, it is evident that where reference is made to phthalic acid, some simple derivative, such as chlorinated phthalic acid, brominated phthalic acid, methylated phthalic acid, or the like, would simply act as a functional equivalent. This applies'not only to phthalic acid, but all the dibasic acids enumerated.

Similarly, it is evident that there is no intention to differentiate between isomeric forms. One isomeric form may serve as well as another. Attention is particularly called to the last two examples above, which are characterized especially by the presence of a free carboxyl radical other than the carboxyl radical derived from dibasic acid. Needless to state, in the reaction between the ester derived by reaction between a polybasic carboxy acid material and a selected fatty material of the kind described, if there be a carboxyl radical attached to a fatty chain available for esterification as well as a carboxyl attached to the dibasic acid, then in such event, if there is suflicient available hydroxyl radicals attached to the amine of the kind previously described, both types of carboxyl radicals, i. e., (a) a carboxyl radical attached to a polybasic carboxy acid residue; and (b) a carboxyl radical attached to a fatty acid residue may enter into the reaction. However, my experience is that the carboxyl radical attached to the polybasic other type of carboxyl radical, although both reactions may take place simultaneously to at least a limited degree.

I desire to emphasize that the products obtained in the above examples may be used in the form of the amine by direct contact with an emulsion without contact with water. It may be contacted with water, i. e., inthe form of a solution so as to produce in a greater or lesser degree the amine base. Furthermore, any of the products above described may be combined with a suitable acid. Acetic acid may be employed. Hydrochloric acid is particularly desirable. In some instances acids, such as oleic acid or naphthenic acid, may be employed to give a suitable salt. As previously pointed out, any carboxylic hydrogen atom may be replaced by a suitable metallic atom or an organic radical derived from an alcohol or from an amine. All such ionizable hydrogen atom equivalents are considered as the functional equivalent of the,

ionizable hydrogen atoms themselves, and such neutralized forms are included in the scope of the appended claims as the equivalent of the acidic form. Theexpression fatty acid compound is employed to include the acid itself, as well as salts and esters thereof. It is realized that where a free carboxyl and a basic amine residue exist in the same molecule, there may be a-tendency towards the formation of inner salts comparable to sulfanilicacid; but due to the size of the molecule involved and perhaps for reasons of steric hindrance, I am not aware that such inner salts are formed.

Briefly, then,the preparation of the composition of matter herein contemplated depends on a reaction involving a polybasic carboxy acid body, or its functional equivalent as described, and the complex amine of the kind described, in such a manner as to involve reactions other than salt formation. In other words, the" complex amines are basic in nature, and therefore could react with a polybasic acid to form a salt in a manner which, for sake of convenience, will be indicated by asomewhat simpler reaction, thus:

coon

nann oocmcoon coon or IRaNHIOOQTIJOONa Such reactionsare purely salt formation. The

materials of the kind herein contemplated, re-

gardless of their nature, are of the kind obtained by reactions other than salt formation, and also other than amidification.

I desire to emphasize that the expression polybasic carboxy acid" as it appears in the claims refers not only to the acid itself, but to any functional equivalent, such as, the anhydride, the acyl chloride, a salt form having at least two free car-bowls, such.as mono-sodium citrate, etc. It is also understood that in the hereto appended claims the nature of the final product is not limited to the form havinga free carboxylic hydrogen, but that such free carboxylic hydrogen may actually be replaced by any functional equivalent of the kind previously described. for instance, a metallic atom, an ammonium radical, an amine radical, such as an amvlamine radical, benzylamine radical, ethanolamine radical, diethanolamine radical, triethanolamine ,radical, a hydrocarbon radical, such as an ethyl, methyl, prcpyl, or amylradical, a radical derived from ethylene glycol, glycerol, or the like; a cyclohexyl radical, benzyl radical, etc. All such forms in which such ionizable hydrogen atom equivalent replaces an'ionizabie hydrogen atom, are obvious functional equivalents.

Attentionls directed to the fact that the wor amldificatiorf'has been applied to the reaction involving the, replacement of an amino hydrogen atom by an acyl radical'without conventional limitation to areaction involving ammonia. The.

ventional nomenclature has been for purposes of simplicity and .to show the similarity between fatty acid compound includes not only the fatty acid itself, but also the salts and esters thereof,

,- be employed as diluents.

leum, etc., may be employed as diluents.

except esters of the kind in which there is a hydroxyl attached to the hydrocarbon radical derived from the esterifying alcohol; i. e., it is not intended to include esters such as monoricinolein, diricinolein, etc., characterized by the presence of a hydroxyl radical attached to the organic radical which replaces the ionizable hydrogen atom of the carboxy radical of the fatty acid. Furthermore, in the hereto appended claims, reference to the product derived by reaction between an acid ester of the kind pre- -viously described and an amine of the kind previously' described, is meant to referto such products in'all its various modifications previously referred to, to-wit, such instances where carboxylic hydrogen atoms appear as such or have been replaced by metallic atoms, organic radicals derived from various alcohols, amine radicals, or residues, .etc.; and as to the presence of any basic amine nitrogen atom, it may be in the amine form or in a salt form or in a-baseform, as, for .example, obtainable by contact with water. The

functional equivalents of all these variations have i been pointed out previously. and were readily comprehended; and the scope of the claims, in light of such obvious equivalents, requires no further discussion.

As to blown oils, blown fatty acids, polymerized oils, polymerized fatty acids, and other similar materials obtained bypxidation, it is understood.

that they may be reacted with the polybasic carboxy acids such as phthalic acid or phthalic anhydride to produce an acidic ester; but it is 'not intended that they should be reacted with amines to produce the intermediate amine which inturn is reacted with the acidic ester derived in part cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petro- Similarly, the material or materials employed as the demulsifying agent of my process maybe admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. materials may be used alone or in admixture with other suitable well known classes of demulsifying agents.

ft is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited water solubility and relatively limited oil solubility. However, since such reagents are sometimes used in aratio of 1 to 10,000 or 1 to 20,000, or even 1 to 30,000, such anapparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is-true in regard to the material or materials employed as the demulsifying agent of my process.

I desire to point out that the superiority of the reagent or demulsifying agent contemplated in- Moreover, said material or' my process is based upon its ability to treat'certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demul'sifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but I have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practicing my process, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combination with other demulsifying procedure, suc as the electrical dehydration process.

The new composition of matter that is employed as the demulsifying agent in my process herein described constitutes the subject-matter of my pending application for patent Serial No. 261,091, filed March 10, 1939.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising products of the kind derivable by esterification reaction between (A) an amine of the formula type in which OH.RCOO represents the oxy-acyl radical derived from a hydroxylated fatty acid; T represents a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 32 carbon atoms; 12 represents a small whole number which is less than 10; m represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or 2, with the proviso that m+m'+m=3; and (B) an acidic ester derived by reaction between a polybasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

, 2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising products of the kind derivable by esterificationmeaction between (A) an amine'of theformula type in which OH.RCOO represents the oxy-acyl radical derived from a hydroxylated fatty acid; T represents a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 32 carbon atoms; m represents the numeral ,1, 2 or 3; m represents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or 2, with the proviso that and (B) an acidic ester derived by reaction between a polybasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid c0m pound being characterized by the absence of any hydroxy hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising products of the kind derivable by esterification reaction between (A) an amine of the formula type (OH.RCOO.C2H4) mN (H) m in which OHRCOO represents the oXy-acyl radical derived from a hydroxylated fatty acid; m represents the numeral 1, 2 or 3; m represents the numeral 0, l or 2, with the proviso that m+m=3; and (B) an acidic ester derived by reaction between a polybasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

4. A process for breaking petroleum emulslons of the water-in-oil type, characterized by subjecting the emulsion to the action of a demu1sifying agent comprising products of the kind derivable by esterification reaction between (A) an amine of the formula type (OHRCOOCzHO mN(H) m in which OH.RCOO represents the oxy-acyl radical derived from ricinoleic acid; m represents the numeral 1, 2 or 3; 111.. represents the numeral 0, 1 or 2, with the proviso that m+m=3; and

(B) an acidic ester derived by reactionbetween a polybasic carboxy acid and a ricinoleic acid compound; said ricinoleic acid compound being characterized by the absence of any hydroxy hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising products of the kind derivable by esterification reaction between (A) an amine of the formula type (OI-IRCOOCzHa) mN(H) m in which OHRCOO represents the oxy-acyl radical derived from ricinoleic acid; m represents the numeral 1, 2 or 3; m represents the numeral 6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub jecting the emulsion to the action of a demulsifying agent comprising products of the kind derivable by esterification reaction between (A) an amine of the formula. type (OHRCOO.C2H4) mN(H) m in which OHRCOO represents the oxy-acyl radimvm DE GROO'I'E. 

